Evaporation of water from a surface (like skin) cools the surface down. Humidity is water (as a gas) is in the air. The more water there is in the air already, the harder it is for water to evaporate into the air. A mister doesn’t add much water to the air as a gas, but it is sprinkling tiny droplets of liquid water around, which gets surfaces wet, then the water evaporates and cools the surfaces.
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